Organic compound, OLED (Organic Light Emitting Diode) with compound and organic light emitting device

Abstract

The invention relates to the technical field of preparation of organic photoelectric materials, in particular to an organic compound, an OLED with the compound and an organic light-emitting device with the compound. According to the organic compound disclosed by the invention, by limiting the combination of an aromatic group, a carbazole structure and a triarylamine mother nucleus, the compound has excellent luminous efficiency and relatively good thermal stability; meanwhile, the organic compound provided by the invention is used as a light-emitting auxiliary layer material for a device, so that the organic light-emitting device can effectively have lower driving voltage and maintain the stability of the voltage, the light-emitting efficiency is improved, the service life is obviously prolonged, and the organic compound has a very good application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of organic photoelectric materials, and in particular to an organic compound, an OLED having the compound, and an organic light-emitting device. Background Art

[0002] Organic light-emitting diodes (OLEDs), also known as organic electroluminescent devices, are a technology that applies voltage to organic electroluminescent elements to inject holes from the anode and electrons from the cathode into the light-emitting layer respectively. The injected holes and electrons recombine to form excitons, resulting in luminescence. It can convert electrical energy into light energy through organic light-emitting materials.

[0003] Existing blue light auxiliary materials are still insufficient in improving device performance. Even if multiple materials are used in combination, display technology still has problems such as high driving voltage and short display life, which seriously affects the further practical application of this technology.

[0004] Therefore, it is necessary to continue to work hard to develop organic light-emitting devices with low voltage drive, high brightness and long life, and to find suitable OLED optoelectronic functional materials for OLED devices to solve the above problems. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides an organic compound, an OLED having the compound, and a display or lighting device. The provided triarylamine compound contains a carbazole structure and is combined with an aromatic group, so that the organic compound is used in an organic electroluminescent device, so that the device can have both high efficiency and long service life.

[0006] The organic compound provided by the present invention is realized by the following technical scheme: An organic compound having a structure shown in the following formula (I): ; Formula (I) In formula (I), R1 is selected from a single bond, a C6-C30 aryl group; R2 is independently selected from hydrogen, a deuterated or undeuterated C6-C30 aryl group, and n is selected from a natural number from 0 to the maximum possible substitution; L1 and L2 are each independently selected from a single bond, a substituted or unsubstituted C6-C30 aryl group; Ar1 ​​and Ar2 are each independently selected from hydrogen, a substituted or unsubstituted C6~C30 aryl group, a substituted or unsubstituted C5-C36 heteroaryl group, and when there is substitution, the substituent is selected from a C1-C24 alkyl group, a C6-C30 aryl group, and the hydrogen atoms of the compound described in formula (I) may be partially or fully deuterated.

[0007] Preferably, in the formula (I), R1 is selected from a single bond, phenyl, biphenyl, and naphthyl; R2 is independently selected from hydrogen, phenyl, and naphthyl; and n is selected from an integer of 0-2.

[0008] Preferably, in the formula (I), L1 and L2 are each independently selected from a single bond, a phenyl group, a biphenyl group, and a naphthyl group; Ar1 ​​and Ar2 are each independently selected from one or more combinations of hydrogen, a phenyl group, a naphthyl group, a phenanthryl group, a naphthylphenyl group, a C1-C4 alkyl group or a C6-C12 aryl group substituted fluorenyl group, a 9,9-dimethylsilylfluorenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazole group, and a phenylcarbazole group.

[0009] According to one or more embodiments, the present invention provides an organic compound selected from any one of the chemical structures shown below: .

[0010] The present invention also provides a use of the above-mentioned device in an organic electroluminescent device.

[0011] The present invention also provides an organic electroluminescent device, the organic electroluminescent device comprising: substrate layer; a first electrode, the first electrode being on the substrate; An organic light-emitting functional layer, the organic light-emitting functional layer is on the first electrode; A second electrode, the second electrode being on the organic light-emitting functional layer; The organic light-emitting functional layer includes a light-emitting auxiliary layer; the light-emitting auxiliary layer includes the organic compound as described above.

[0012] The present invention also provides a composition, which comprises the organic compound described in formula (I).

[0013] The present invention also provides a preparation, which comprises an organic compound having a structure as shown in the above formula (I) or a composition as described above and at least one solvent. The solvent is not particularly limited, and can be used as unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, butyl chloride, butyl bromide, pentyl chloride, pentyl bromide, hexyl chloride, hexyl bromide, cyclohexyl chloride, cyclohexyl bromide, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran, tetrahydropyran, and ester solvents such as alkyl benzoate.

[0014] The organic electroluminescent device of the present invention can be used in an OLED lighting or display device.

[0015] The present invention also provides a display or lighting device, which comprises one or more of the organic electroluminescent devices described above.

[0016] In summary, compared with the prior art, the present invention has the following beneficial effects: The organic compound of the present invention is limited to a carbazole group and an aryl-substituted carbazole group and an aromatic group to obtain a triarylamine compound, so that the compound has excellent luminous efficiency and a good service life; at the same time, the organic compound provided by the present invention is used in a device, which can effectively make the organic light-emitting device have a lower driving voltage and maintain voltage stability, and the luminous efficiency is improved, and the working life of the device can also be better. DETAILED DESCRIPTION

[0017] The following will be described clearly and completely in conjunction with the technical solutions of the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0018] The aryl group of the present invention refers to a general term for a monovalent group after removing a hydrogen atom from the aromatic core carbon of an aromatic hydrocarbon molecule, which can be a monocyclic aryl group or a condensed ring aryl group. The aryl group can be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples may include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthyl, anthracenyl, phenanthrenyl or pyrenyl, but are not limited thereto. Aryl or aromatic group-as used herein, non-condensed and condensed systems are considered. The aryl group can be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, phenanthrene, fluorene, pyrene, perylene and azulene, with preference given to phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4"-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl and m-quaterphenyl.

[0019] The heteroaryl group of the present invention refers to a general term for a group obtained by replacing one or more aromatic carbon atoms in an aromatic group with a heteroatom, wherein the heteroatom includes but is not limited to oxygen, sulfur, silicon or nitrogen atoms, and the heteroaryl group may be a monocyclic heteroaryl group or a condensed ring heteroaryl group, and may be a heteroaryl group having 6 to 30 carbon atoms, preferably a heteroaryl group having 6 to 20 carbon atoms. Examples may include pyridyl, pyrrolyl, pyridyl, thienyl, furanyl, indolyl, quinolyl, isoquinolyl, benzothienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, etc., but are not limited thereto.

[0020] The alkyl group of the present invention includes straight chain and branched chain alkyl groups. It can be an alkyl group having 1 to 24 carbon atoms, and preferably an alkyl group having 1 to 4 carbon atoms, including methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, etc. In addition, the alkyl group can be optionally substituted.

[0021] Throughout the specification, unless explicitly described to the contrary, "comprising" any component will be understood to imply the inclusion of other elements, rather than excluding any other elements. In addition, it should be understood that throughout the specification, when an element such as a layer, film, region or substrate is referred to as being "on" or "above" another element, it can be "directly on" another element, or there may be intervening elements. In addition, "on..." or "above..." means being located above the target portion, and does not necessarily mean being located above according to the direction of gravity.

[0022] An object of the present invention is to provide an organic electroluminescent device, which includes: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; a second electrode, which is on the organic light-emitting functional layer; the organic light-emitting functional layer includes a light-emitting auxiliary layer, and the light-emitting auxiliary layer includes a triarylamine compound having a carbazole structure fragment.

[0023] In one embodiment of the present invention, the luminescence auxiliary layer in the organic electroluminescent (OLED) device comprises one or more components of the compound represented by the above general formula (I) as luminescence auxiliary materials.

[0024] In a preferred embodiment of the present invention, an OLED is provided, which includes a substrate, an anode, a cathode, and an organic light-emitting functional layer, wherein the organic light-emitting functional layer may include a light-emitting layer, a light-emitting auxiliary layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, etc., or may only include a light-emitting layer and one or more other layers; wherein the light-emitting auxiliary layer comprises one or more of the compounds represented by the above general formula (I). Optionally, there is a covering layer, a protective layer and / or an encapsulation layer on the organic light-emitting functional layer.

[0025] The substrate of the present invention can be any substrate used in a typical organic light-emitting device. It can be a glass or transparent plastic substrate, or a substrate of an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproofness. Depending on the properties of the substrate, the use direction is different.

[0026] As materials for the hole injection layer, the hole transport layer, the electron injection layer, and the light emitting layer, any material can be selected from known related materials used for OLED devices.

[0027] The present invention is described in detail below in conjunction with specific examples. Synthesis Examples All raw materials and solvents are commercially available unless otherwise specified, and the solvents are used directly without further treatment.

[0028] Example

[0029] Example 1: Synthesis of Compound 001 Synthesis route: ; Synthesis method: 1) Add 003-1 (10 mmol), 003-2 (25 mmol), sodium tert-butoxide (10 mmol), and 200 mL of toluene to the reaction flask. After nitrogen replacement, add PD2 (DBA) 3 (5 × 10 -2 mmoL), Sphos(5×10 -2 mmoL), heat to 100-120°C, reflux for 6 hours, and stop the reaction. Cool to 30-40°C, add 200mL of water, and separate into layers. After washing twice, concentrate toluene, add 100mL of n-heptane, and slurry. Obtain the intermediate product 003-3; 2) Add 003-3 (10 mmol), 003-4 (25 mmol), sodium tert-butoxide (10 mmol), and 200 mL of toluene to the reaction flask. After nitrogen replacement, add pd2(dba)3 (5×10 -2 mmoL), Sphos(5×10 -2 mmoL), heated to 100-120°C, refluxed for 6 hours, and then stopped the reaction. Cooled to 30-40°C, added 200mL of water, and separated into layers. After washing with water twice, concentrated toluene, added 100mL of n-heptane, and slurried. The target product 003 was obtained; The structure of the test target product 003: LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 738.30, and the test value was 738.86.

[0030] Example 2: Synthesis of Compound 005 Referring to the synthesis steps and reaction conditions of Example 1, compound 005 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 778.30 and the test value was 778.92.

[0031] Example 3: Synthesis of Compound 009 Compound 009 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 828.31 and the test value was 828.95.

[0032] Example 4: Synthesis of Compound 011 Compound 011 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was analyzed by liquid chromatography-mass spectrometry: the theoretical value was 738.30 and the test value was 738.88.

[0033] Example 5: Synthesis of Compound 022 Referring to the synthesis steps and reaction conditions of Example 1, compound 022 was synthesized, and LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 794.28, and the test value was 794.90.

[0034] Example 6: Synthesis of Compound 023 Compound 023 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 802.33 and the test value was 802.97.

[0035] Example 7: Synthesis of Compound 024 Referring to the synthesis steps and reaction conditions of Example 1, compound 024 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 846.34 and the test value was 846.98.

[0036] Example 8: Synthesis of Compound 025 Referring to the synthesis steps and reaction conditions of Example 1, compound 025 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 788.32 and the test value was 788.96.

[0037] Example 9: Synthesis of Compound 028 Compound 028 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 894.32 and the test value was 894.94.

[0038] Example 10: Synthesis of Compound 030 Referring to the synthesis steps and reaction conditions of Example 1, compound 030 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 727.30 and the test value was 727.86.

[0039] Example 11: Synthesis of Compound 034 Compound 034 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 778.30 and the test value was 778.92.

[0040] Example 12: Synthesis of Compound 043 Compound 043 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 728.32 and the test value was 728.90.

[0041] Example 13: Synthesis of Compound 045 Compound 045 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 853.35 and the test value was 853.97.

[0042] Example 14: Synthesis of Compound 050 Referring to the synthesis steps and reaction conditions of Example 1, compound 050 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 778.30 and the test value was 778.94.

[0043] Example 15: Synthesis of Compound 052 Referring to the synthesis steps and reaction conditions of Example 1, compound 052 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 854.33 and the test value was 854.95.

[0044] Example 16: Synthesis of Compound 056 Referring to the synthesis steps and reaction conditions of Example 1, compound 056 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 853.35 and the test value was 853.93.

[0045] Several examples of the application of the organic compound of the present invention in OLED devices are listed below to further illustrate the beneficial effects of the compound of the present invention. The materials used in the examples are purchased from commercial sources or synthesized by the user.

[0046] Fabrication of OLED devices:

[0047] As a reference preparation method for a device embodiment, the present invention evaporates 50-500nm ITO / Ag / ITO on an alkali-free glass substrate as an anode, evaporates a hole injection layer (5nm-20nm), a hole transport layer (50-150nm), a light-emitting auxiliary layer (5-120nm), a light-emitting layer (20-50nm), a hole blocking layer (5-20nm), an electron transport layer (20-80nm), and an electron injection layer (1-10nm) on the anode, and then co-evaporates Mg and Ag (weight ratio 1:9, 100-150nm) to make a semi-transparent cathode, and then evaporates a cover layer compound. Finally, the light-emitting device is encapsulated using an epoxy resin adhesive in a nitrogen atmosphere.

[0048] In a preferred specific embodiment, the structure of the OLED device provided by the present invention is as follows: first, an alkali-free glass substrate is washed with isopropanol using an ultrasonic cleaner for 15 minutes, and then a UV ozone cleaning treatment is performed in the air for 30 minutes. The treated substrate is vacuum-deposited with ITO / Ag / ITO 100nm as an anode, and then a hole injection layer (HT:PD, 10nm, 2%), a hole transport layer (HT, 130nm), a light-emitting auxiliary layer (compound 003, 5nm), a blue light-emitting layer (main material: doping material = BH:BD (weight ratio 98:2, 30nm)), a hole blocking layer (HBL, 5nm), an electron transport layer (ET: Liq=1:1, 30nm), and an electron injection layer (Yb, 1nm) are sequentially stacked and evaporated, and Mg and Ag (weight ratio 1:9, 130nm) are co-evaporated to make a semi-transparent cathode, and then a compound CPL (65nm) is evaporated as a covering layer. Finally, the light emitting device is encapsulated with epoxy resin adhesive in a nitrogen atmosphere, which is recorded as Application Example 1. The molecular structure formula of the relevant material is as follows (particularly preferably selected from the following structure, but it does not mean that the present invention is limited to the following structure): .

[0049] The method provided in the above-mentioned application example 1 was used to prepare application examples 2 to 16 and comparative example 1, the only difference being that the compounds listed in Table 1 were used as luminescent auxiliary materials to replace compound 003 in application example 1. The structure of Ref-1 used in the comparative example is as follows: .

[0050] Performance evaluation of OLED devices:

[0051] The current of the OLED device at different voltages was tested using a Keithley 2365A digital nanovoltmeter, and the current was then divided by the luminous area to obtain the current density of the OLED device at different voltages. The brightness and radiant energy flux density of the OLED device at different voltages were tested using a Konicaminolta CS-2000 spectroradiometer. Based on the current density and brightness of the OLED device at different voltages, the current density (10 mA / cm 2 ) working voltage Volt and current efficiency (cd / A), BI=E / CIEy, refers to the Blue Index in blue light, and is also a parameter for measuring the luminous efficiency of blue light. E refers to the current efficiency, and CIEy refers to the vertical coordinate color point obtained by bringing the wavelength of the device's luminous half-peak width into the CIE1930 software. The test data is shown in Table 1.

[0052] As can be seen from Table 1, compared with Comparative Example 1, Application Examples 1 to 16 have lower operating voltage, higher BI luminous efficiency and longer service life. The performance improvement of each application example is based on the fact that the organic compound material of the present invention has better thermal stability and auxiliary transmission ability. The luminescent auxiliary material in the present invention combines the nitrogen-containing heterocyclic ring of the carbazole structure with the aromatic group, and has a large conjugated plane, so that the compound has good thermal stability and a higher glass transition temperature, and improves the service life of the device; at the same time, the replacement of the carbazole group with an aromatic group can have a greater impact on the luminescent properties of the compound, thereby improving the luminous efficiency of the device, and can better achieve the balance of electron and hole transmission and the exciton conversion rate, and reduce the power consumption of the device.

[0053] This specific embodiment is merely an explanation of the present invention and is not a limitation of the present invention. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed. However, as long as they are within the scope of the claims of the present invention, they are protected by the patent law.

Claims

1. An organic compound, characterized in that The organic compound has a structure shown in the following formula (I): ； Formula (I) In formula (I), R1 is selected from a single bond, a phenyl group, and a naphthyl group; R2 is independently selected from hydrogen, a deuterated or undeuterated C6-C30 aryl group, and n is selected from a natural number from 0 to the maximum possible substitution; L1 and L2 are each independently selected from a single bond, a substituted or unsubstituted C6-C30 aryl group; Ar1 ​​and Ar2 are each independently selected from hydrogen, a substituted or unsubstituted C6~C30 aryl group, or a substituted or unsubstituted C5-C36 heteroaryl group. When there is substitution, the substituent is selected from a C1-C24 alkyl group and a C6-C30 aryl group. The hydrogen atoms of the compound described in formula (I) may be partially or fully deuterated.

2. The organic compound according to claim 1, characterized in that In the formula (I), R1 is selected from a single bond, phenyl, and naphthyl; R2 is independently selected from hydrogen, phenyl, and naphthyl; and n is selected from an integer of 0-2.

3. The organic compound according to claim 1, characterized in that In the formula (I), L1 and L2 are each independently selected from a single bond, a phenyl group, a biphenyl group, and a naphthyl group; Ar1 ​​and Ar2 are each independently selected from one or more combinations of hydrogen, a phenyl group, a naphthyl group, a phenanthryl group, a naphthylphenyl group, a C1-C4 alkyl group or a C6-C12 aryl group substituted fluorenyl group, a 9,9-dimethylsilylfluorenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazole group, and a phenylcarbazole group.

4. The organic compound according to claim 1, characterized in that The organic compound is selected from any one of the following chemical structures: 。 5. Use of the organic compound according to any one of claims 1 to 4 in the preparation of an organic electroluminescent device.

6. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises: substrate layer; a first electrode, the first electrode being on the substrate; An organic light-emitting functional layer, the organic light-emitting functional layer is on the first electrode; A second electrode, the second electrode being on the organic light-emitting functional layer; The organic light-emitting functional layer includes a light-emitting auxiliary layer; the light-emitting auxiliary layer includes the organic compound according to any one of claims 1 to 4.

7. A composition, characterized in that The composition comprises the organic compound according to any one of claims 1 to 4.

8. A preparation, characterized in that The preparation comprises the organic compound according to any one of claims 1 to 4 and at least one solvent.

9. Use of the organic electroluminescent device according to claim 6 in a display or lighting device.

10. A display or lighting device, characterized in that: The device comprises the organic electroluminescent device as claimed in claim 6.

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